WO2024033089A1 - Électrolyte composite solide - Google Patents

Électrolyte composite solide Download PDF

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Publication number
WO2024033089A1
WO2024033089A1 PCT/EP2023/070753 EP2023070753W WO2024033089A1 WO 2024033089 A1 WO2024033089 A1 WO 2024033089A1 EP 2023070753 W EP2023070753 W EP 2023070753W WO 2024033089 A1 WO2024033089 A1 WO 2024033089A1
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lithium
solid
composite electrolyte
sulfide
solid composite
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PCT/EP2023/070753
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English (en)
Inventor
Vincent FINSY
Eliana Ieva
Alessio Marrani
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Solvay Specialty Polymers Italy S.P.A.
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Publication of WO2024033089A1 publication Critical patent/WO2024033089A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers

Definitions

  • the present invention relates to a solid composite electrolyte comprising a) at least one fluoropolymer and b) at least one sulfide-based solid ionic conducting inorganic particle, wherein a) the fluoropolymer comprises recurring units derived from i) at least 50.0 mol% of vinylidene difluorides (VDF), the mol% being relative to the total moles of recurring units; ii) at least one C2-C8 chloro and/or bromo and/or iodo fluoroolefin; and iii) at least one C2-C8 fluoroolefin, wherein i), ii) and iii) are different from each other; to a slurry for manufacturing a solid composite electrolyte comprising a) at least one fluoropolymer according to the present invention and b) a sulfide- based solid ionic conducting inorganic particle, and c) at
  • Li-ion batteries have retained dominant position in the market of rechargeable energy storage devices for decades, thanks to their many benefits such as light-weight, reasonable energy density and good cycle life. Nonetheless, better safety and higher energy density have been continuously required pursuant to the development of high power applications such as electrical vehicles, hybrid electrical vehicles, grid energy storage, etc.
  • Solid-state batteries have been believed to be the next generation of energy storage devices, where the highly flammable liquid electrolyte is replaced by a solid-state electrolyte that the risk of ignition and/or explosion can be substantially removed.
  • solid-state electrolytes organic polymer, inorganics and composites have been actively investigated, each of which has its own pros and cons.
  • the composites i.e. inorganic solid electrolytes dispersed into polymers, e.g.
  • Fluorinated polymers such as VDF-based polymers have been widely used as binders in conventional Li-ion batteries. Thanks to their good oxidative resistance, they have been mostly applied in electrode-forming formulations of Li-ion batteries, in particular for a positive electrode, and their use as binders for sulfide-based solid-state electrodes and/or electrolyte layers have been also actively studied in this field.
  • US 10511052 B2 discloses fluorinated polymers, such as VDF- hexafluoropropylene (HFP), VDF-tetrafluoroethylene (TFE), VDF-HFP-TFE, and TFE-HFP as binders for sulfide-based solid electrolytes.
  • HFP VDF- hexafluoropropylene
  • TFE VDF-tetrafluoroethylene
  • TFE-HFP-TFE VDF-HFP-TFE
  • TFE-HFP binders for sulfide-based solid electrolytes.
  • JP 5675694 B2 (Kureha and Toyota) describes a method for manufacturing sulfide-based solid electrolyte-containing electrodes and electrolyte layers, which comprise a fluorinated polymer as a binder, in particular VDF-based copolymers having from 40 to 70 mol% of VDF content, for instance VDF- HFP, VDF-chlorotrifluoroethylene (CTFE), VDF-TFE-HFP, preferably VDF- TFE-HFP.
  • VDF-based copolymers having from 40 to 70 mol% of VDF content, for instance VDF- HFP, VDF-chlorotrifluoroethylene (CTFE), VDF-TFE-HFP, preferably VDF- TFE-HFP.
  • VDF-based/fluorinated binders exhibit low cohesive strength among solid electrolyte particles and/or electroactive materials inside solid electrolyte layers and/or electrodes.
  • relatively high content of binders are applied into the solid electrolyte layers and electrodes, which results in a large reduction of ionic conductivity.
  • Another critical issue is that VDF-based/fluorinated binders exhibit low adhesion strength toward the current collectors, resulting in electrode delamination and eventually battery failure.
  • US 2015/096169 A1 discloses that a positive electrode for a sulfide-based solid-state battery, which is formed with a slurry containing a fluorine-based copolymer having a specific amount of VDF units (between 40 and 70 mol%), exerts good adhesion towards a current collector.
  • US’169 embodies VDF-TFE-HFP (55/25/20 in mol%) as a binder exhibiting higher adhesion compared to an amino-modified hydrogenated binder.
  • WO 2021/039950 (Fujifilm) describes that an inorganic solid electrolytecontaining composition comprising an inorganic solid electrolyte, a polymeric binder and a dispersion medium, wherein the polymeric binder comprises a fluorine-based copolymer that contains a VDF component and from 21 to 65 mol% of HFP component, exhibits more than 60% of adsorption to inorganic solid electrolytes and is effective in controlling excessive increase of viscosity, re-coagulation or sedimentation of inorganic particles that a solid-state battery having superior cycling properties can be achieved.
  • WO’950 proposes the use of specific functional groups such as carboxylic acid group, phosphoric acid group, and hydroxyl group in a VDF- HFP copolymer.
  • CN 113451638A (Qingtao Kunshan Energy Development Co. Ltd.) describes a sulfide-based solid electrolyte membrane, characterized in that the membrane comprises a polymer film with a 3D structure and a sulfide-based solid electrolyte, manufactured by electrospinning of a membrane and subsequent infiltration of sulfide materials thereto.
  • Said polymer film is either a VDF-based copolymer, represented as VDF-A, or a VDF-based terpolymer, represented as VDF-A-B, wherein A is selected from the group consisting of trifluoroethylene (TrFE), HFP and methyl methacrylate, and B is selected from the group consisting of CTFE, 1 ,1- chlorofluoroethylene and chlorodifluoroethylene.
  • CN’638A merely embodies VDF-TrFE copolymer only and moreover does not provide any further insight concerning a fluoropolymer with optimal combination of at least three different monomers and a solvent compatible with sulfide materials.
  • a gel polymer electrolyte composed of a plasticized VDF- HFP-CTFE terpolymer, wherein an organic carbonate mixture is absorbed in a conventional Li-ion battery as a liquid electrolyte is disclosed in Jarvis et. al.
  • the use of novel VDF-HFP-CTFE terpolymers in lithium-ion polymer cells (Journal of Power Sources 119-121 (2003) 465-468), where it’s also described that the introduction of CTFE to VDF-HFP increases the capacity for electrolyte uptake thanks to its low melt flow index, while maintaining structural integrity, in comparison with PVDF homopolymer and VDF-HFP copolymer.
  • Jarvis et. al. provides no clue at all regarding its use as a binder for a solid-state battery, e.g. in a sulfide-based solid composite electrolyte.
  • a first object of the present invention is a solid composite electrolyte comprising a) at least one fluoropolymer and b) at least one sulfide-based solid ionic conducting inorganic particle, wherein a) the fluoropolymer comprises recurring units derived from i) at least 50.0% by mol (mol%) of vinylidene difluorides (VDF), the mol% being relative to the total moles of recurring units, ii) at least one C2-C8 chloro and/or bromo and/or iodo fluoroolefin, and iii) at least one C2-C8 fluoroolefin, wherein i), ii) and iii) are different from each other.
  • VDF vinylidene difluorides
  • a second object of the present invention is a slurry for manufacturing a solid composite electrolyte comprising a) a fluoropolymer and b) a sulfide-based solid ionic conducting inorganic particle, and c) at least one non-aqueous solvent.
  • a third object of the present invention is an electrode comprising the solid composite electrolyte according to the present invention, d) at least one electroactive material, and optionally e) at least one conductive agent.
  • a fourth object of the present invention is a solid state battery comprising a positive electrode, a negative electrode and a membrane that is positioned between the positive electrode and the negative electrode, wherein at least one of the positive electrode, the negative electrode and the membrane comprises a solid composite electrolyte according to the present invention, optionally d) at least one electroactive material and/or e) at least one conductive agent.
  • a fifth object of the present invention is a binder solution for a solid state battery comprising a) at least one fluoropolymer according to the present invention and c) at least one non-aqueous solvent.
  • the solid composite electrolyte according to the present invention may deliver a particularly advantageous combination of properties, e.g. excellent adhesion of an electrode towards a current collector and significantly enhanced cohesive strength within a membrane, while maintaining good ionic conductivity, notably by using a fluoropolymer according to the present invention.
  • Figure 1 is a cross-section of the pressure cell in AC impedance spectroscopy, developed within Solvay to measure the ionic conductivity of the film.
  • the film is pressed between 2 stainless steel electrodes during impedance measurement.
  • Figure 2 represents an equivalent circuit for modelling conductivity behaviours of solid composite electrolytes, wherein R1 and R2 represent the bulk and grain boundary resistance respectively, and Q2 and Q3 represent the grain boundary and electrode contributions respectively.
  • Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or subranges encompassed within that range as if each numerical value and subrange is explicitly recited.
  • percent by weight indicates the content of a specific component in a mixture, calculated as the ratio between the weight of the component and the total weight of the mixture.
  • concentration of recurring units in ‘percent by mol’ (mol%) refers to the concentration relative to the total number of recurring units in the polymer, unless explicitly stated otherwise.
  • the present invention provides a solid composite electrolyte comprising: a) at least one fluoropolymer; and b) at least one sulfide-based solid ionic conducting inorganic particle; wherein a) the fluoropolymer comprises recurring units derived from: i) at least 50.0% by mol (mol%) of vinylidene difluorides (VDF), the mol% being relative to the total moles of recurring units; ii) at least one C2-C8 chloro and/or bromo and/or iodo fluoroolefin; and iii) at least one C2-C8 fluoroolefin, wherein i), ii) and iii) are different from each other.
  • VDF vinylidene difluorides
  • i) vinylidene difluorides account for at least 60.0 mol%, the mol% being relative to the total moles of recurring units.
  • i) vinylidene difluorides account for at least 70.0 mol%, the mol% being relative to the total moles of recurring units.
  • the C2-C8 chloro and/or bromo and/or iodo fluoroolefins is selected from the group consisting of 1 ,1- chlorofluoroethylene (CFE), chlorodifluoroethylene (CDFE), bromotrifluoroethylene, chlorotrifluoroethylene (CTFE), 1 ,2-dichloro-1 ,2- difluoroethylene, iodotrifluoroethylene, and combinations thereof.
  • the C2-C8 chloro and/or bromo and/or iodo fluoroolefin is c/s-1 ,2-dichloro-1 ,2-difluoroethylene or trans-'i ,2-dichloro-1 ,2- difluoroethylene, preferably trans-'i ,2-dichloro-1 ,2-difluoroethylene.
  • the C2-C8 chloro and/or bromo and/or iodo fluoroolefin is CTFE.
  • the C2-C8 fluoroolefin is selected from the group consisting of:
  • C2-C8 perfluoroolefins such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP); hydrogen-containing C2-C8 fluoroolefins, such as vinyl fluoride (VF), trifluoroethylene (TrFE), hexafluoroisobutylene;
  • (per)fluorooxyalkyl vinylethers of formula CF2 CFOX, wherein X is a C1-C12 ((per)fluoro)oxyalkyl comprising at least one catenary oxygen atom;
  • the C2-C8 fluoroolefin is selected from the group consisting of vinyl fluoride (VF), trifluoroethylene (TrFE), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), hexafluoroisobutylene, and combinations thereof.
  • the C2-C8 fluoroolefin is HFP.
  • the C2-C8 fluoroolefin is TrFE.
  • the fluoropolymer further comprises recurring units derived from:
  • C2-C8 non-fluorinated olefins such as ethylene, propylene
  • the hydrophilic (meth)acrylic monomer is selected from the group consisting of acrylic acid (AA), methacrylic acid (MA), hydroxyethyl (meth)acrylate, 2-hydroxypropyl acrylate, hydroxyethylhexyl (meth)acrylate, butyl acrylate, and the like as well as combinations thereof.
  • the fluoropolymer comprises recurring units derived from C2-C8 non-fluorinated olefins and/or hydrophilic (meth)acrylic monomer in an amount from 0.1 to 10.0 mol%, preferably from 0.2 to 5.0 mol%, more preferably from 0.2 to 2.0 mol%, the mol% being relative to the total moles of recurring units.
  • the hydrophilic (meth)acrylic monomer is AA.
  • the hydrophilic (meth)acrylic monomer is MA.
  • the fluoropolymer is a terpolymer of VDF- CTFE-HFP.
  • the fluoropolymer is a terpolymer of VDF- CTFE-TrFE.
  • the fluoropolymer is a tetrapolymer of VDF-CTFE-HFP-AA.
  • the fluoropolymer may be manufactured by suspension or emulsion polymerization process.
  • the fluoropolymer is a fluoroelastomer.
  • fluoroelastomer is intended to designate a fluoropolymer resin serving as a base constituent for obtaining a true elastomer.
  • True elastomers are defined by the ASTM, Special Technical Bulletin, No. 184 standard as materials capable of being stretched, at room temperature, to twice their intrinsic length and which, once they have been released after holding them under tension for 5 minutes, return to within 10% of their initial length in the same time.
  • a fluoroelastomer is amorphous, exhibits a low degree of crystallinity, i.e. having crystalline phase less than 20 vol%, and has a glass transition temperature (T g ) below room temperature.
  • T g glass transition temperature
  • a fluoroelastomer has advantageously a T g below 10°C, preferably below 5°C, more preferably below 0°C, even more preferably below -5°C.
  • amorphous is hereby intended to denote a polymer having a heat of fusion of less than 5.0 J/g, preferably of less than 3.0 J/g, and more preferably of less than 2.0 J/g as measured by Differential Scanning Calorimetry (DSC) at a heating rate of 10°C/min according to ASTM D3418.
  • DSC Differential Scanning Calorimetry
  • the term “sulfide-based solid ionic conducting inorganic particle” is not particularly limited as long as it is a solid electrolyte material containing sulfur atom(s) in the molecular structure or in the composition.
  • the sulfide-based solid ionic conducting inorganic particle preferably contains Li, S, and an element of from 13 to 15 groups, for instance, P, Si, Sn, Ge, Al, As, Sb, or B, to increase Li-ion conductivity.
  • the sulfide-based solid ionic conducting inorganic particle according to the present invention is preferably selected from the group consisting of:
  • LSPS lithium tin phosphorus sulfide
  • LPS lithium phosphorus sulfide
  • LPS lithium -doped LPS
  • Li2CuPS4 Lii+2xZni- x PS4, wherein 0 ⁇ x ⁇ 1
  • Li3.33Mgo.33P2S6, and Li4-3 X Sc x P2Se wherein 0 ⁇ x ⁇ 1 ;
  • LPSO lithium phosphorus sulfide oxygen
  • LiXPSO lithium phosphorus sulfide oxygen including X
  • X is Si, Ge, Sn, As, or Al
  • LSS lithium silicon sulfide
  • Li2SiSs Li2S-P2Ss-SiS2 , Li2S-P2S5-SiS2-LiCI, Li2S-SiS2-P2Ss, Li2S-SiS2-P2Ss-Lil, Li2S-SiS2-Lil, Li2S-SiS2, Li9.54Sii.74Pi.44Sn.7Clo.3, and Li2S-SiS2-Al2S3j
  • lithium boron sulfide materials such as LisBSs and Li2S-B2Ss-Lil ;
  • lithium tin sulfide materials and lithium arsenide materials such as Lio.8Sno.8S2, Li4SnS4, Li3.833Sno.833Aso.i66S4, LisAsS4-Li4SnS4, and Ge-substituted LisAsS4;
  • Li a PSbX c lithium phosphorus sulfide materials of general formula Li a PSbX c , wherein X represents at least one halogen element selected from the group consisting of Cl, Br and I or a combination thereof; and a represents a number from 2.0 to 7.0, b represents a number from 3.5 to 6.0, and c represents a number from 0 to 3.0, such as Li4PS4CI, Li7P2SsCI, and Li7P2Ssl ; and
  • the sulfide-based solid ionic conducting inorganic particle is a lithium phosphorus sulfide material of the above general formula Li a PSbX c , more particularly Argyrodite-type sulfide material of formula LiePSsX, wherein X is Cl, Br or I.
  • the Argyrodite-type sulfide material of formula LiePSsY is deficient in sulfur and/or lithium, for instance Lie-xPSs- xC +x with 0 ⁇ x ⁇ 0.5, or doped with a heteroatom.
  • Particularly preferred sulfide-based solid ionic conducting particles are lithium tin phosphorus sulfide (“LSPS”) materials (e.g. LiioSnP2Si2) and Argyrodite-type sulfide materials (e.g. LiePSsCI).
  • LSPS lithium tin phosphorus sulfide
  • Argyrodite-type sulfide materials e.g. LiePSsCI
  • an amount of b) the sulfide-based solid ionic conducting inorganic particle is at least 40.0 wt%, preferably at least 60.0 wt%, more preferably at least 70 wt%, much more preferably at least 80.0 wt%, and most preferably at least 90.0 wt%, and/or at most 99.8 wt%, preferably at most 99.5 wt%, more preferably at most 99.0 wt%, and most preferably at most 98.0 wt%, based on the total weight of the solid composite electrolyte.
  • the amount of b) the sulfide-based solid ionic conducting inorganic particle is from 40.0 to 99.8 wt%, preferably from 60.0 to 99.5 wt%, more preferably from 70.0 to 99.0 wt%, even more preferably from 80.0 to 99.0 wt%, and most preferably from 90.0 to 99.0 wt%, based on the total weight of the solid composite electrolyte.
  • the amount of b) the sulfide-based solid ionic conducting inorganic particle is from 95.0 to 99.0 wt%, based on the total weight of the solid composite electrolyte.
  • At least one sulfide-based solid ionic conducting inorganic particle differs from a lithium salt, conventionally used as an essential element of a lithium secondary battery.
  • lithium salt is hereby intended to denote a substance which needs to be dissolved in a solvent to ensure ionic conduction.
  • a liquid electrolyte consists mainly of lithium salts in a non-aqueous organic solvent where lithium ions (i.e. Li + cations) are used as charge carriers such that the liquid electrolyte acts as a conductive pathway for the movement of cations, i.e. Li + cations passing from the cathode to anode during the discharge.
  • the dissolution of a lithium salt is through solvent-Li + interactions, i.e. the dissociation of Li + cation- (counter)anion interaction is critical.
  • Non-limitative examples of a lithium salt include, notably, lithium hexafluorophosphate (LiPFe), lithium perchlorate (LiCICU), lithium hexafluoroarsenate (LiAsFe), lithium hexafluoroantimonate (LiSbFe), lithium hexafluorotantalate (LiTaFe), lithium tetrachloroaluminate (LiAICk), lithium tetrafluoroborate (I BF4), lithium chloroborate (Li2BioCI-io), lithium fluoroborate (Li2BioFio), lithium trifluoromethane sulfonate (IJCF3SO3), lithium bis(fluorosulfonyl)imide Li(FSO2)2N (LiFSI), lithium bis(trifluoromethanesulfonyl)imide Li(SO2CFs)2N (LiTFSI), and mixtures thereof.
  • LiPFe lithium
  • the Li + cation conductivity originates from both the total ionic conductivity and the cation transference number. Given that the cation transference number in a non-aqueous organic solvent is low, e.g. usually smaller than 0.5, the ionic conductivity plays a critical role in the battery performance.
  • a liquid electrolyte where at least one lithium salt is dissolved in at least one non-aqueous organic solvent plays a pivotal role as one of the major components of a conventional lithium secondary battery.
  • a solid electrolyte is an ionic conductor which delivers ions between two electrodes. Unlike the liquid electrolyte, however, a solid electrolyte does not require to be dissociated/dissolved into Li + cations in order to render the solid electrolyte conductive.
  • the lithium positions within LiePSsX form localized cages where multiple jump processes are possible, i.e. doublet jump, intracage jump and intercage jump, by which Li + cation diffusion/transport occurs (Sulfide and oxide inorganic solid electrolytes for All-Solid-State Li Batteries: Nanomaterials 2020, 10, 1606; doi:10.3390/nano 10081606 by Reddy et. al.). That is, unlike liquid electrolytes, only one species in a solid electrolyte is mobile and the structures have partial site occupancies of said mobile species, i.e. Li + cations, corresponding to cooperative conduction mechanism.
  • a lithium salt clearly differs from a sulfide-based solid ionic conducting inorganic particle containing lithium species in its inorganic structure in that a lithium salt needs to be dissolved in a solvent to ensure ionic conduction, while a sulfide-based solid ionic conducting inorganic particle has an intrinsic ionic conductivity above 0.1 mS/cm at room temperature that is due to the diffusion of a sub-lattice of mobile lithium species in its inorganic framework.
  • the solid composite electrolyte does not contain a lithium salt.
  • the solid composite electrolyte of the present invention is characterized by high adhesion properties towards a current collector, when it is used in manufacturing an electrode of a solid-state battery, for instance a positive electrode.
  • the nature of the “current collector” depends on whether the electrode thereby provided is either a positive electrode or a negative electrode.
  • the current collector typically comprises, preferably consists of at least one metal selected from the group consisting of Aluminium (Al), Nickel (Ni), Titanium (Ti), and alloys thereof, preferably Al.
  • the current collector typically comprises, preferably consists of at least one metal selected from the group consisting of Lithium (Li), Sodium (Na), Zinc (Zn), Magnesium (Mg), Copper (Cu) and alloys thereof, preferably Cu.
  • a second object of the present invention is a slurry for manufacturing a solid composite electrolyte comprising a) at least one fluoropolymer, b) at least one sulfide-based solid ionic conducting inorganic particle, and c) at least one non-aqueous solvent.
  • the fluoropolymer is as defined in the present invention.
  • the non-aqueous solvent is able to dissolve a) the fluoropolymer and is compatible with b) the sulfide-based solid ionic conducting inorganic particle, meaning the solvent has no negative impact on the ionic conductivity of the resulting solid composite electrolyte.
  • the non-aqueous solvent is selected from the group consisting of nitrile-containing solvents, ethers, esters, thiols, thioethers, ketones, and tertiary amines.
  • the non-aqueous solvent is a nitrile containing solvent with general formula of R-CN, where R represents an alkyl group.
  • R-CN nitrile containing solvent with general formula of R-CN, where R represents an alkyl group.
  • nitrile-containing solvents are acetonitrile, butyronitrile, valeronitrile, isobutylnitrile and the like.
  • the non-aqueous solvent is an ether with general formula of R1-O-R2, where R1 and R2 represent independently an alkyl group.
  • R1 and R2 represent independently an alkyl group.
  • Included in the ether solvents are cyclic ethers based on 3, 5 or 6-membered rings.
  • the cyclic ethers can be substituted with alkyl groups, can have unsaturation and can have additional functional elements such as nitrogen or oxygen atoms inside the ring.
  • Non-limiting examples of (cyclic) ether solvents are diethylether, 1 ,2-dimethoxyether, cyclopentyl methyl ether, diethyl ether, dibutyl ether, 1 ,3-dioxolane, anisole, tetrahydrofuran, methyl tetrahydrofuran, tetrahydropyran and the like.
  • the non-aqueous solvent is an ester with general formula of R3-COO-R4, where R3 and R4 represent independently an alkyl group.
  • ester solvents are butyl butyrate, ethyl benzoate and the like.
  • the cyclic thioethers can be substituted with alkyl groups, can have unsaturation and can have additional functional elements such as nitrogen or oxygen atoms inside the ring.
  • thiol solvents are ethanethiol, tert-dodecyl mercaptan, thiophenol, tert-butyl mercaptan, octanethiol, dimethylsulfide, ethylmethylsulfide, methyl benzylsulfide and the like.
  • ketone solvents are methyl ethyl ketone, methyl isobutyl ketone, di-isobutyl ketone, acetophenone, benzophenone and the like, preferably methyl isobutyl ketone.
  • the non-aqueous solvent is a tertiary amine with general formula of R10R11R12N, where R10, R11 and R12 represent independently an alkyl group.
  • the N atom of the tertiary amine can be buried inside a 3, 5 or 6 membered ring.
  • Non-limiting examples of tertiary amine solvents are triethylamine, dimethylbutylamine, tributylamine, cyclohexyldimethylamine, N-ethylpiperidine and the like.
  • the alkyl groups of R1 to R12 respectively refer to “alkyl groups” including saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclic alkyl groups (or "cycloalkyl” or "alicyclic” or “carbocyclic” groups), such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, branched-chain alkyl groups, such as isopropyl, tert-butyl, sec-butyl, and isobutyl, and alkylsubstituted alkyl groups, such as alkyl-substituted cycloalkyl groups and cycloalky
  • alkyl groups may include functional groups such as 1 or more unsaturation, ether, carbonyl, carboxyl, hydroxyl, thio, thiol, thioxy, sulfo, nitrile, nitro, nitroso, azo, amide, imide, amino, imino or halogen.
  • functional groups such as 1 or more unsaturation, ether, carbonyl, carboxyl, hydroxyl, thio, thiol, thioxy, sulfo, nitrile, nitro, nitroso, azo, amide, imide, amino, imino or halogen.
  • the non-aqueous solvent comprises nitrile- containing solvents, such as acetonitrile; ethers, such as tetrahydrofuran, 2- methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 1 ,3-dioxolane, diethyl ether and 1 ,2-dimethoxyether; esters, such as butyl butyrate; and ketones such as methyl isobutyl ketone.
  • solvents such as acetonitrile
  • ethers such as tetrahydrofuran, 2- methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 1 ,3-dioxolane, diethyl ether and 1 ,2-dimethoxyether
  • esters such as butyl butyrate
  • ketones such as methyl isobutyl ketone.
  • the non-aqueous solvent is an ester, such as butyl butyrate.
  • the non-aqueous solvent is a ketone, such as methyl isobutyl ketone.
  • the slurry may further comprise a second solvent, for instance saturated hydrocarbons and aromatic hydrocarbons such as, but not limited to, linear and branched alkanes (e.g. heptane), cyclic alkanes (e.g. cyclohexane), and aromatics (e.g. xylene and toluene).
  • a second solvent for instance saturated hydrocarbons and aromatic hydrocarbons such as, but not limited to, linear and branched alkanes (e.g. heptane), cyclic alkanes (e.g. cyclohexane), and aromatics (e.g. xylene and toluene).
  • the slurry can be suitably prepared by a process comprising mixing a) a fluoropolymer, b) a sulfide-based solid ionic conducting inorganic particle and c) a non-aqueous solvent by any method known to the person skilled in the art.
  • the slurry is prepared by a process comprising solubilizing a) a fluoropolymer in c) a non-aqueous solvent followed by adding c) a sulfide-based solid ionic conducting inorganic particle, and mixing the resulting mixture.
  • the amount of a) a fluoropolymer in a slurry is such to provide a solid composite electrolyte including a) the fluoropolymer in an amount ranging at least 1.0 wt%, preferably at least 1.5 wt%, more preferably 2.0 wt%, and/or at most 20.0 wt%, preferably at most 15.0 wt%, more preferably at most 10.0 wt%, most preferably at most 5.0 wt% with respect to the total weight of a) the fluoropolymer and b) the sulfide-based solid ionic conducting inorganic particle.
  • the amount of a) a fluoropolymer in a slurry is such to provide a solid composite electrolyte including a) the fluoropolymer in an amount ranging from 1.0 to 20.0 wt%, preferably from 1.5 to 15.0 wt%, more preferably from 2.0 to 10.0 wt%, and most preferably 2.0 to 5.0 wt% with respect to the total weight of a) the fluoropolymer and b) the sulfide- based solid ionic conducting inorganic particle. Accordingly, the resulting solid composite electrolyte exhibits good cohesion between a) the fluoropolymer and b) the sulfide-based solid ionic conducting inorganic particle, while maintaining good ionic conductivity.
  • the slurry according to the present invention is typically applied onto at least one foil of inert flexible support by a technique selected from casting, spray coating, rotating spray coating, roll coating, doctor blading, slot die coating, gravure coating, ink-jet printing, spin coating, and screen printing.
  • the wet film so obtained typically has a thickness of from 10 to 400 pm, preferably from 50 to 200 pm.
  • the wet film is then dried at a temperature between 10°C and 200°C, preferably between 20°C and 80°C.
  • An additional drying step in an oven under vacuum at a temperature between 20°C and 150°C, preferably between 50°C and 80°C, can be suitably carried out to completely remove the solvent.
  • the skilled person in the art may select the optimal duration and temperature of the drying step, in consideration of the boiling point of the solvent.
  • the dry film thusly- obtained can be further subject to an additional compression step, such as calendaring, uniaxial or isostatic compression process, to lower the porosity and to increase the density of the solid composite electrolyte.
  • the slurry may further comprise d) at least one electroactive material, and optionally e) at least one conductive agent.
  • the electroactive material is for a positive electrode.
  • the term “positive electrode” is intended to denote, in particular, the electrode of an electrochemical cell, where reduction occurs during discharging, while the term “negative electrode” is intended to denote, in particular, the electrode of an electrochemical cell, where oxidation occurs during discharging.
  • the term “electroactive material” is intended to denote a material that is able to incorporate or insert into its structure and substantially release therefrom lithium ions during the charging and discharging phases in a battery.
  • the electroactive material for a positive electrode is not particularly limited. It may comprise a composite metal chalcogenide of formula LiMGte, wherein M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr, and V and Q is a chalcogen such as O and S.
  • M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr, and V and Q is a chalcogen such as O and S.
  • a lithium-based composite metal oxide of formula IJMO2 wherein M is the same as defined above.
  • Preferred examples thereof may include LiCoC , LiNiC>2, LiNi x Coi- x O2 (0 ⁇ x ⁇ 1), and spinel-structured LiMn2O4.
  • the electroactive material of a positive electrode may comprise a lithiated or partially lithiated transition metal oxyanion-based electroactive material of formula MiM2(JO4)fEi-f, wherein Mi is lithium, which may be partially substituted by another alkali metal representing less that 20% of the Mi metals, M2 is a transition metal at the oxidation level of +2 selected from Fe, Mn, Ni or mixtures thereof, which may be partially substituted by one or more additional metals at oxidation levels between +1 and +5 and representing less than 35% of the M2 metals, including 0, JO4 is any oxyanion wherein J is either P, S, V, Si, Nb, Mo or a combination thereof, E is a fluoride, hydroxide or chloride anion, f is the molar fraction of the JO4 oxyanion, generally comprised between 0.75 and 1.
  • the MiM2(JO4)fEi-f electroactive material as defined above is preferably phosphate-based and may have an ordered or modified olivine structure.
  • the electroactive material of a positive electrode has formula Li3- x M’ y M”2- y (JO4)3 wherein 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 2, M’ and M” are the same or different metals, at least one of which being a transition metal, JO4 is preferably PO4 which may be partially substituted with another oxyanion, wherein J is either S, V, Si, Nb, Mo or a combination thereof.
  • M is at least one metal selected from Co, Ni, Fe, Mn, Cr and V and Q is O or S
  • LiNi x Coi- x O2 (0 ⁇
  • the electroactive material is for a positive electrode and is selected from the group consisting of NMC, NCA, NCO, and LNMO.
  • the term “conductive agent” is intended to denote, in particular, a material which is used to ensure electrodes have good charging and discharging performance and to provide additional electrical conductivity.
  • the conductive agent are carbonaceous materials and metal powders or fibers, for instance carbon blacks, carbon nanotubes (CNT), vapor-grown carbon fibers (VGCF), graphite, graphene, graphite fibers and the like.
  • carbon blacks include Ketjen black and acetylene black.
  • the metal powders or fibers include nickel and aluminium powders or fibers.
  • the amount of a) a fluoropolymer in a slurry is such to provide a solid composite electrolyte including a) the fluoropolymer in an amount ranging from 1.0 to 20.0 wt%, preferably from 1.5 to 15.0 wt%, more preferably from 2.0 to 10.0 wt%, and most preferably 2.0 to 5.0 wt% with respect to the total weight of a) the fluoropolymer, b) the sulfide-based solid ionic conducting inorganic particle, c) the electroactive material and optionally e) at least one conductive agent. Accordingly, the resulting electrode exhibits outstanding adhesion towards a current collector.
  • a third object of the present invention is an electrode comprising a solid composite electrolyte according to the present invention, d) at least one electroactive material, and optionally e) at least one conductive agent.
  • d) the electroactive materials is for a positive electrode.
  • an electrode comprises at least one fluoropolymer according to the present invention, at least one electroactive material for a positive electrode, and at least one sulfide-based solid ionic conducting inorganic particle.
  • a positive electrode comprises VDF-CTFE-HFP terpolymer as a fluoropolymer, LiePSsCI as a sulfide-based solid ionic conducting inorganic particle, LiNio.6Mno.2Coo.2O2 as an electroactive material for a positive electrode, and optionally a carbon black as a conductive agent.
  • a positive electrode comprises VDF- CTFE-TrFE terpolymer as a fluoropolymer, LiePSsCI as a sulfide-based solid ionic conducting inorganic particle, LiNio.6Mno.2Coo.2O2 as an electroactive material for a positive electrode, and optionally a carbon black as a conductive agent.
  • a positive electrode comprises VDF- CTFE-HFP-AA as a fluoropolymer, LiePSsCI as a sulfide-based solid ionic conducting inorganic particle, LiNio.6Mno.2Coo.2O2 as an electroactive material for a positive electrode, and optionally a carbon black as a conductive agent.
  • a fourth object of the present invention is a solid state battery comprising a positive electrode, a negative electrode, and a membrane that is positioned between the positive electrode and the negative electrode, wherein at least one of the positive electrode, the negative electrode and the membrane comprises a solid composite electrolyte according to the present invention, optionally d) at least one electroactive material and/or e) at least one conductive agent.
  • a fifth object of the present invention is a binder solution for a solid state battery comprising a) at least one fluoropolymer according to the present invention and c) at least one non-aqueous solvent.
  • the non-aqueous solvent is as defined in the present invention.
  • a person skilled in the art may easily select the proper amount of c) a nonaqueous solvent in order to achieve uniform dissolution of a) a fluoropolymer and suitable evaporation of the same, when a binder solution according to the present invention is used in manufacturing a solid composite electrolyte.
  • This solid composite electrolyte may be used either as a membrane positioned between a positive electrode and a negative electrode or as an electrode for solid state batteries.
  • C-NERGYTM SUPER C65T Commercially available from Imerys
  • BB Butyl butyrate
  • MIBK Methyl isobutyl ketone
  • VDF-CTFE-HFP 80.0/10.0/10.0 in mol%), synthesized within Solvay Specialty Polymers Italy S.p.A
  • VDF-CTFE-HFP (79.0/15.0/6.0 in mol%), synthesized within Solvay Specialty Polymers Italy S.p.A - Polymer 3: VDF-CTFE-HFP-AA (78.7/9.9/9.9/0.5 in mol%), synthesized within Solvay Specialty Polymers Italy S.p.A
  • VDF-CTFE-TrFE 63.5/7.5/29.0 in mol%)
  • Solvene®300 commercially available from Solvay Specialty Polymers Italy S.p.A
  • VDF-HFP 78.5/21.5 mol%)
  • VDF-TFE-HFP (60.0/20.0/20.0 in mol%)
  • Tecnoflon® T538 commercially available from Solvay Specialty Polymers Italy S.p.A
  • VDF-TFE-HFP (65.0/19.0/16.0 in mol%)
  • Tecnoflon® TN commercially available from Solvay Specialty Polymers Italy S.p.A.
  • (NH4)2S20s) solution in ethyl acetate (3% w/w) and 2.0 mL of pure ethyl acetate was fed into the autoclave.
  • the polymerization pressure was maintained constant until the polymerization ended.
  • 200.0 g of the mixture was fed, the feeding was stopped, the reactor was cooled down to room temperature and degassed in order to remove the residual.
  • the latex as produced was discharged and further degassed with nitrogen for 24 hours.
  • the resulting polymer was isolated by using standard isolation procedure with aluminum sulfate (Ah(SO4)3) and then dried in a vented oven for 24 hours at 90°C.
  • Polymer 2 was synthesized in a similar way as Polymer 1. After 1.3L of demineralized water was introduced, the temperature was brought to reaction temperature of 75°C. 3.8 x 10 5 Pa (absolute) of VDF and 4.0 x 10 5 Pa (absolute) of HFP were introduced. The gaseous mixture of VDF-CTFE- HFP in a nominal molar ratio of 79.0/15.0/6.0 was added by using a compressor, until reaching a pressure of 20.0 x 10 5 Pa (absolute).
  • composition of the gaseous mixture present in the autoclave head was 78.3 mol% of VDF, 14.6 mol% of CTFE, and 7.1 mol% of HFP, before starting the reaction. 45.0 cc of ammonium persulfate solution in ethyl acetate (3% w/w) and 3 mL of pure ethyl acetate were fed into the autoclave.
  • the polymerization pressure was maintained constant until the polymerization ended.
  • 300.0 g of the mixture was fed, the feeding was stopped, the reactor was cooled down to room temperature and then degased in order to remove the residual.
  • the latex as produced was discharged and further degassed with nitrogen for 24 hours. Then the resulting polymer was isolated by using standard isolation procedure with aluminum sulfate and dried in a vented oven for 24 hours at 90°C.
  • 10 mL of ammonium persulfate solution in ethyl acetate (3% w/w) and 5.0 mL of acrylic acid solution (2% w/w) were fed into the autoclave, per every 20.0 g of polymerization.
  • the polymerization pressure was maintained constant until the polymerization ended.
  • 200.0 g of said gaseous mixture was fed, the feeding was stopped and the reactor was cooled down to room temperature.
  • the latex as produced was discharged and frozen for 48 hours.
  • the resulting polymer after being molten, was washed with demineralized water and dried in a vented oven for 48 hours at 80°C.
  • the wet film was dried at 50°C on a hot plate for one hour and then placed in an oven at 80°C under vacuum during the night.
  • the samples were stored in a minigrip bag and then placed in a sealed bag. All experiments were performed in an Argon- filled glove box.
  • the solid composite electrolyte of E5 was prepared in the same manner as E1 , except that MIBK was used as a solvent instead of BB.
  • the solid composite electrolyte of E2 was prepared in the same manner as E1 , except that Polymer 2 was used instead of Polymer 1.
  • the solid composite electrolyte of E6 was prepared in the same manner as E2, except that MIBK was used as a solvent instead of BB.
  • the solid composite electrolyte of E3 was prepared in the same manner as E1 , except that Polymer 3 was used instead of Polymer 1.
  • the solid composite electrolyte of E7 was prepared in the same manner as E3, except that MIBK was used as a solvent instead of BB.
  • the solid composite electrolyte of E4 was prepared in the same manner as E1 , except that Polymer 4 was used instead of Polymer 1 .
  • the solid composite electrolyte of CE1 was prepared in the same manner as E1 , except that Polymer 5 was used instead of Polymer 1.
  • the solid composite electrolyte of CE2 was prepared in the same manner as CE1 , except that MIBK was used as a solvent instead of BB.
  • the solid composite electrolyte of CE3 was prepared in the same manner as E1 , except that Polymer 6 was used instead of Polymer 1 .
  • the solid composite electrolyte of CE4 was prepared in the same manner as E1 , except that Polymer 7 was used instead of Polymer 1 .
  • a dry, free standing solid composite electrolyte in strip was fixed on a rigid Al plate (2.6 cm*10 cm) using a double-sided tape (width 25mm; thickness 0.24mm).
  • a motorized tension/compression force test stand ESM303 from Mark-10 Corporation
  • ESM303 motorized tension/compression force test stand
  • a second doublesided tape (diameter: 1 cm & thickness: 0.24 mm), fixed at the bottom of the round tip, was pressed with a force of 200 N for 1 min to the second surface of the solid composite electrolyte.
  • the tip was removed (pulled-off) from the surface of the solid composite electrolyte with a constant speed of 100 mm/s.
  • the impedance spectra were determined at a pressure of 370 MPa and a temperature of 20°C.
  • the AC impedance measurements were performed with a potentiostate (VMP-300, BioLogic Science Instruments SAS) in the frequency range of 1000 Hz to 4.7 MHz.
  • the Nyquist plot of the soild composite electrolytes showed the typical behaviour of a solid electrolyte (inorganic, polymer or composite) with a semicircle and Warburg-type impedance in the high and low frequency region respectively.
  • the conductivity behaviour of the composite electrolyte was modelled according to the equivalent circuit R1 (R2/Q2)Q3 (see Figure 2) in which R is a resistance and Q a constant phase element, wherein R1 and R2 represent the bulk and grain boundary resistance respectively, and Q2 and Q3 the grain boundary and electrode contributions respectively.
  • the intercept of the semicircle with the real axis at high frequency is attributed to the bulk resistance (R1) and the intercept with the real axis at lower frequency is attributed to the total resistance (R1 + R2) of the films.
  • the ionic conductivity of the solid composite electrolytes of E1 -E4, CE1 , CE4 & CE5 was recorded in Table 1 .
  • Positive electrodes of E1-E4, CE1 , CE3 and CE4 composed of 74.0 pbw of NMC622, 20.0 pbw of LPSCI, 2.0 pbw of conductive carbon black, and 4.0 pbw of a fluoropolymer (selected from Polymers 1 to 7) were produced as the following:
  • a 10.0 wt% of a binder solution was prepared by weighing 1.0 g of a fluoropolymer and 9.0 g of BB. Subsequently, 1.0 g of LPSCI, 0.1 g of conductive carbon, 3.7 g of NMC622 and 2.0 g of the 10.0 wt% of the binder solution were mixed with 4 glass balls under magnetic stirring at 400 rpm for a minimum of 6 hours. The slurry as obtained was cast on an Al current collector by using an automatic film applicator from Elcometer Ltd.
  • the solid content of the slurry and the casting speed were adapted in order to maintain the slurry viscosity during casting between 2.0 and 10.0 Pa.s and in order to obtain a dry electrode loading of from 25.0 to 30.0 mg/cm 2 .
  • the wet film was dried at 50°C on a hot plate for one hour, placed in an oven at 80°C under vacuum during the night, stored in a minigrip bag, and then placed in a sealed bag. The experiment was performed in an Argon-filled glove box.
  • Positive electrodes of E5-E7 and CE2 were produced in the same manner as above described, except that MIBK was used as a solvent instead of BB.
  • the adhesion strength of the positive electrode to the Al current collector was evaluated using a 180° peel test.
  • An electrode strip (2 cm*10 cm) of the dried electrode was fixed with the electrode facing down and the current collector facing up on a rigid Al plate (2.6 cm*10 cm) using a double sided tape (width 25mm; thickness 0.24mm).
  • the Al current collector was peeled off from the electrode using a motorized tension/compression force test stand (ESM303 from Mark-10 Corporation), maintaining an angle of 180° and at a constant speed of 300 mm/min.
  • ESM303 motorized tension/compression force test stand
  • the force needed to remove the Al current collector from the electrode was recorded in Table 1 as an average value of 3 independent strips, generated from 3 independent electrodes using 3 independent slurries with the same composition. Peel- off tests were performed in a dry room with dew point of -40°C.

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Abstract

La présente invention concerne un électrolyte composite solide comprenant a) au moins un fluoropolymère et b) au moins une particule inorganique conductrice ionique solide à base de sulfure, a) le fluoropolymère comprenant des motifs récurrents dérivés i) d'au moins 50,0 % en moles de difluorures de vinylidène, le % en moles étant par rapport au nombre total de moles de motifs récurrents ; ii) d'au moins une chloro et/ou bromo et/ou iodo fluorooléfine en C2-C8 ; et iii) d'au moins une fluorooléfine en C2-C8, i), ii) et iii) étant différents les uns des autres ; une bouillie pour la fabrication d'un électrolyte composite solide comprenant a) au moins un fluoropolymère selon la présente invention et b) une particule inorganique conductrice ionique solide à base de sulfure, et c) au moins un solvant non aqueux ; une électrode comprenant un électrolyte composite solide selon la présente invention, d) au moins un matériau électroactif, et éventuellement e) au moins un agent conducteur ; et une batterie à l'état solide comprenant une électrode positive, une électrode négative et une membrane, parmi lesquelles au moins l'une comprend un électrolyte composite solide selon la présente invention. La présente invention concerne également une solution de liant pour une batterie à l'état solide comprenant a) au moins un fluoropolymère selon la présente invention et c) au moins un solvant non aqueux.
PCT/EP2023/070753 2022-08-10 2023-07-26 Électrolyte composite solide WO2024033089A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130264522A1 (en) * 2010-12-22 2013-10-10 Solvay Specialty Polymers Italy S.P.A. Vinylidene fluoride copolymers
JP5675694B2 (ja) 2011-08-25 2015-02-25 トヨタ自動車株式会社 電解質層・電極積層体の製造方法、及び硫化物系固体電池の製造方法
US20150096169A1 (en) 2012-05-31 2015-04-09 Kureha Corporation Slurry for positive electrode for sulfide-based solid-state battery, positive electrode for sulfide-based solid-state battery and method for manufacturing the same, and sulfide-based solid-state battery and method for manufacturing the same
US10511052B2 (en) 2011-11-30 2019-12-17 Idemitsu Kosan Co., Ltd. Electrolyte sheet
WO2021039950A1 (fr) 2019-08-30 2021-03-04 富士フイルム株式会社 Composition contenant un électrolyte solide inorganique, feuille pour batteries secondaires à semi-conducteur, batterie secondaire à semi-conducteur et procédés de production de batterie secondaire à semi-conducteur et feuille pour batteries secondaires à semi-conducteur
US20210098847A1 (en) * 2018-09-28 2021-04-01 Lg Chem, Ltd. Separator for lithium secondary battery with improved adhesiveness towards electrode and resistance characteristics and lithium secondary battery comprising the separator
CN113451638A (zh) 2021-07-22 2021-09-28 清陶(昆山)能源发展股份有限公司 一种硫化物固态电解质膜及固态锂离子电池
EP3940846A1 (fr) * 2020-07-17 2022-01-19 Solvay SA Électrolyte composite solide

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130264522A1 (en) * 2010-12-22 2013-10-10 Solvay Specialty Polymers Italy S.P.A. Vinylidene fluoride copolymers
JP5675694B2 (ja) 2011-08-25 2015-02-25 トヨタ自動車株式会社 電解質層・電極積層体の製造方法、及び硫化物系固体電池の製造方法
US10511052B2 (en) 2011-11-30 2019-12-17 Idemitsu Kosan Co., Ltd. Electrolyte sheet
US20150096169A1 (en) 2012-05-31 2015-04-09 Kureha Corporation Slurry for positive electrode for sulfide-based solid-state battery, positive electrode for sulfide-based solid-state battery and method for manufacturing the same, and sulfide-based solid-state battery and method for manufacturing the same
US20210098847A1 (en) * 2018-09-28 2021-04-01 Lg Chem, Ltd. Separator for lithium secondary battery with improved adhesiveness towards electrode and resistance characteristics and lithium secondary battery comprising the separator
WO2021039950A1 (fr) 2019-08-30 2021-03-04 富士フイルム株式会社 Composition contenant un électrolyte solide inorganique, feuille pour batteries secondaires à semi-conducteur, batterie secondaire à semi-conducteur et procédés de production de batterie secondaire à semi-conducteur et feuille pour batteries secondaires à semi-conducteur
EP3940846A1 (fr) * 2020-07-17 2022-01-19 Solvay SA Électrolyte composite solide
CN113451638A (zh) 2021-07-22 2021-09-28 清陶(昆山)能源发展股份有限公司 一种硫化物固态电解质膜及固态锂离子电池

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF POWER SOURCES, vol. 119-121, 2003, pages 465 - 468
REDDY, NANOMATERIALS, vol. 10, 2020, pages 1606

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